Oxoalkyl esters

ABSTRACT

Described is a genus of compounds defined according to the structure: ##STR1## wherein Z represents carbinol having the structure: ##STR2## or carboxaldehyde having the structure: ##STR3## and wherein R represents 3-heptanyl or phenyl produced by (i) reacting a carboxylic acid with 2,2-dimethyl-1,3-propanediol to form the compound wherein Z represents carbinol; (ii) and then, if desired, subsequently reacting the resulting alcohol to form an aldehyde; and organoleptic uses of such compounds in the field of perfumery, colognes and perfumed articles (e.g. perfumed polymers, or solid or liquid anionic, cationic, nonionic or switterionic detergents, fabric softener compositions, drier-added fabric softener articles, hair preparations, hair sprays, bath preparations and the like).

This is a divisional of application Ser. No. 307,366, filed Oct. 1,1981, now U.S. Pat. No. 4,368,145.

BACKGROUND OF THE INVENTION

The instant invention relates to the compounds defined according to thegeneric structure: ##STR4## wherein Z represents carbinol having thestructure: ##STR5## or carboxaldehyde having the structure: ##STR6## andwherein R represents 3-heptanyl or phenyl and the use of these compoundsin augmenting or enhancing the aroma of perfumes, colognes and perfumedartcles.

Inexpensive chemical compounds which can provide intense andlong-lasting ozoney, aldehydic, floral, green, spicy (coriander-like,cardamom-like, ginger-like), fruity, honey, tobacco, coumarin-like,cumene-like and woody aromas are high desirable in the art of perfumery.Many of the natural materials which provide such fragrances andcontribute such desired nuances to perfumery compositions are high incost, unobtainable at times, vary in quality from one batch to another,have toxic properties and/or are generally subject to the usualvariations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree or they contribute undesirable or unwanted odorto the compositions.

Oxyalkanals are known in the art of perfumery, e.g. geranoxyacetaldehyde, is a well known perfume ingredient.

Indeed, U.S. Pat. No. 3,992,457 issued on Nov. 16, 1976 discloses theuse of certain oxyalkanals as intermediates in the production ofcompounds useful in perfumery. These oxyalkanals are prepared accordingto the reaction: ##STR7##

The compounds of the prior art, however, do not have the advantageousand unobvious properties in the perfume industry that the compounds ofthe instant application having the above defined generic structure have.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I whichcontains the compound having the structure: ##STR8##

FIG. 2 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR9##

FIG. 3 is the NMR spectrum for the distillation product of the reactionproduct of Example I which consists of the compound having thestructure: ##STR10##

FIG. 4 is the infra-red spectrum for the distillation product of thereaction product of Example I consisting of the compound having thestructure: ##STR11##

FIG. 5 is the GLC profile for the reaction product of Example IIconsisting of the compound having the structure: ##STR12##

FIG. 6 is the NMR spectrum for the distillation product of the reactionproduct of Example II consisting of the compound having the structure:##STR13##

FIG. 7 is the infra-red spectrum for the distillation product of thereaction product of Example II consisting of the compound having thestructure: ##STR14##

FIG. 8 is the NMR spectrum for the distillation product of the reactionproduct of Example III consisting of the compound having the structure:##STR15##

FIG. 9 is the infra-red spectrum for the distillation product of thereaction product of Example III consisting of the compound having thestructure: ##STR16##

FIG. 10 is a schematic diagram of the apparatus used in order to carryout the oxidation reactions of Examples III and V in order to effect thechemical reactions: ##STR17## showing the production of aldehydes byoxidizing alcohols.

FIG. 11 is the GLC profile of the reaction product of Example IVcontaining the compound having the structure: ##STR18##

FIG. 12 is the GLC profile for fraction 3 of the distillation product ofthe reaction product of Example IV consisting of the compound having thestructure: ##STR19##

FIG. 13 is the NMR spectrum for fraction 3 of the distillation productof the reaction product of Example IV containing the compound having thestructure: ##STR20##

FIG. 14 is the infra-red spectrum for the distillation product of thereaction product of Example IV containing the compound having thestructure: ##STR21##

FIG. 15 is the GLC profile for the reaction product of Example Vcontaining the compounds having the structure: ##STR22##

FIG. 16 is the GLC profile for the distillation product (fraction 1) ofthe reaction product of Example V consisting of the compound having thestructure: ##STR23## (conditions: SE-30 column programmed at 100°-220°C.).

FIG. 17 is the NMR spectrum for the trap of peak 101 of the GLC profileof FIG. 14 which is the compound having the structure: ##STR24##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 10 represents a schematic diagram of the process equipment forcarrying out the processes of Example III for effecting the reaction:##STR25## and for Example V effecting the reaction: ##STR26## whereinspecific alcohols are oxidized over a silver catalyst to form specificaldehydes.

In each case, organic reactant feed 100 which is the alcohol reactantdefined according to one of the structures: ##STR27## held in holdingtank 101 calibrated according to calibration apparatus 107 using pump104 is fed through tube 109 simultaneously with water feed 103 held inholding tank 102 calibrated by calibration apparatus 106 (using pump 105for the water feed and tube 108 for the water feed) through vaporizers110 (for the alcohol feed) and 111 (for the water feed) (wherein themixture is heated) and then through heated tube 112 equipped withpressure gauge 113 and relief valve 114 into reaction tube 17 containingcatalyst 18 (the reaction tube being heating using a cylindrical furnace16 at 115). The catalyst bed 18 is rotated as a result of rotation ofthe rotatable rod 19. Simultaneously, air held in pressurized cylinder120 under pressure and nitrogen held in pressurized cylinder 121 arepumped through regulator 119 (for the air) and regulator 122 (for thenitrogen) and filter 118 (for the air) and filter 123 (for the nitrogen)using mass flow controller 117 (for the air) and mass flow controller116 (for the nitrogen) into heated tube 112 thereby creating a mixtureat 112 of air, nitrogen, one of the compounds defined according to oneof the structures: ##STR28## and water vapor. The reaction mixturepasses through catalyst bed 18 through condensation coil 6 which iscooled using cooling water entering the heat exchanger 5 at location 4and exiting at location 7. The condensed reaction product which is oneof the aldehydes: ##STR29## is retained in flask 2 in location 1, flask2 being cooled using ice bath 3. Vacuum source 14 is used to assist theflow of the organic feed, the water feed, the nitrogen and the air oroxygen through reactor 17 into flask 2. Volatiles are condensed in flask12, cooled by dry ice bath 13, and in the Dewar dry ice bath 15.Assisting in the cooling of the volatiles not retained in flask 2 isheat exchanger 9 wherein water is used as a coolant entering the heatexchanger at location 10 and exiting from the heat exchanger at location11.

THE INVENTION

The present invention provides the oxoalkyl esters defined according tothe structure: ##STR30## wherein A represents 3-heptanyl having thestructure: ##STR31## or phenyl and Z represents carbinol having thestructure: ##STR32## or carboxaldehyde having the structure: ##STR33##specifically defining the four compounds having the structures:##STR34##

The compositions of matter of our invention produced according to theprocess of our invention are capable of augmenting, enhancing orproviding ozoney, aldehydic, floral, green, spicy (coriander-like,cardamom-like, ginger-like), fruity, honey-like, tobacco, coumarin-like,cumene-like and woody aroma profiles in perfume compositions, colognesand perfumed articles (e.g. perfume polymers E P or G, acrylic polymers,solid or liquid anionic, cationic, nonionic or zwitterionic detergents,fabric softener articles, fabric softener compositions, drier-addedfabric softener articles, cosmetic powders, hair preparations, bathpreparations, e.g. bath oils and shampoos and the like).

The substances of our invention are produced by first reacting anappropriate aldehyde with 2,2-dimethyl-1,3-propanediol to form either ahydroxyalkyl ester or a cyclic acetal depending on whether benzaldehydeis used as a reactant or whether the initial reactant is a carboxylicacid derivative such as 2-ethyl-hexanoic acid.

Thus, in carrying out the reaction between an aldehyde such asbenzaldehyde and 2,2-dimethyl-1,3-propanediol, the first substance whichis produced is the cyclic acetal according to the reaction: ##STR35##

In order to produce the hydroxyalkyl ester having the structure:##STR36## it is then necessary to oxidize this cyclic acetal using anoxidizing agent. Such an oxidizing agent is an alkali metalhypochlorite, for example, sodium hypochlorite. Thus, when using such anoxidizing agent, the reaction from the cyclic acetal to the hydroxyalkylester is thus: ##STR37##

The resulting alcohol can be used "as is" for its organolepticproperties or it can be further oxidized to form the aldehydes of ourinvention according to, for example, the reaction: ##STR38##

On the other hand, instead of using as a starting material an aldehyde,an alkanoic acid can be used, and in this case, the hydroxyalkyl esteris formed directly by reacting 2,2-dimethyl-1,3-propanediol with, forexample, 2-ethylhexanoic acid in the presence of an acid catalyst or anesterification catalyst, thusly: ##STR39## The resulting hydroxyalkylester can be used "as is" or it, too, can be further oxidized usingoxygen or air to the aldehyde of our invention having the structure:##STR40##

In general, when an aldehyde is used as a starting material, thereaction must go through the cyclic acetal prior to oxidation thereof toform the hydroxyalkyl ester which is then oxidized, if preferred, to thealdehyde according to the general reaction: ##STR41##

When an alkanoic acid or benzoic acid is used as a starting material, inreacting with the 2,2-dimethyl-1,3-propanediol, the hydroxyalkyl esteris formed directly according to the following reaction: ##STR42##wherein R represents 3-heptyl or phenyl.

THE PROCESS OF OUR INVENTION USING THE ALDEHYDE AS A STARTING MATERIAL

The initial reaction to form the cyclic acetal thusly: ##STR43## (forexample) preferably takes place at reflux conditions and mosteconomically at atmospheric pressure. It is preferred that the moleratio of aldehyde:2,2-dimethyl-1,3-propanediol be between 1.5 molesdiol:0.5 moles aldehyde up to 0.5 moles diol:1.5 moles aldehyde with amost preferred mole ratio of diol:aldehyde of about 1:1 (with, however,a slight excess of diol over aldehyde). The reaction should take placein the presence of a solvent which is inert to the reactants and suchsolvents are toluene and xylene. The solvent should be such that itsboiling point at atmospheric pressure is sufficient to cause thereaction to proceed in a reasonable amount of time with a relativelyhigh (greater than 50%) yield of product. Thus, when using toluene as asolvent, the reaction proceeds at a temperature of between 100° and 140°C. depending upon the pressure over the reaction mass during thereaction procedure.

The oxidation of the cyclic acetal to form the hydroxyalkyl esteraccording to, for example, the reaction: ##STR44## preferably takesplace at a temperature of between 10° C. and 40° C.; most preferably atroom temperature, e.g. 22°-30° C. at atmospheric pressure. The moleratio of oxidizing agent:cyclic acetal is preferably 1:1 with a slightexcess of cyclic acetal over the oxidizing agent to ensure that noresidual oxidizing agent remains in the reaction product. Thus, forexample, when reacting the benzaldehyde neopentyl acetal withhypochlorite solution, it is most preferred to use a 10% sodiumhypochlorite solution to react with the benzaldehyde neopentyl acetaland it is also preferred to use a weak acid medium (e.g. a pH of betweenabout 2 and 5). In order to effect such a pH range in the reaction mass,it is preferred to use acetic acid although propionic acid or butyricacid or dilute chloroacetic acid may also be used in order to adjust thepH. In addition, one molar ammonium chloride may be used in place of theacetic acid in order to effect this pH range of the reaction mass.

No matter which way the hydroxyalkyl ester is produced, the conversionof the hydroxyalkyl ester to the desired ester-aldehyde derivative iscarried out in the same way; using oxygen or air and a silver catalystor a copper chromite catalyst at a temperature in the range of from200°-500° C. (atmospheric pressure).

Thus, the oxidation reaction to form the aldehyde: ##STR45## wherein Rrepresents 3-heptyl or phenyl is preferably carried out in apparatusdescribed in the "Detailed Description of the Drawings" section of theinstant specification, supra, and schematically shown in FIG. 5. Theoxidation may use either air or oxygen. The oxidation catalyst mayeither be silver or copper chromite (CUCRO₃).

The reaction temperature may vary from 200° C. up to 500° C. but thetemperature is dependent upon the desired yield and required residencetime of the mixture of compounds defined according to the structure:##STR46## in contact with the solid catalyst. Necessarily, the reactionis vapor phase and the surface area of catalyst and flow rate ofreactants as well as residence time and reaction temperature andpressure are all important variables which must be optimized in relationto one another if yield and conversion of product are to be optimized.It is preferred that the reaction be carried out in the presence ofwater vapor and it is also preferred that the water flow rate and flowrate of alcohol reactant be approximately equal. The gas flow rates mayvary between 50 and 400 ml per minute with a preferred oxygen flow rateof 210-300 ml per minute at a temperature of reaction of 450° C.; aliquid alcohol flow rate of about 2 ml per minute and a water flow rateof about 2 ml per minute. The yield using the foregoing conditions ofproduct defined according to the generic structure: ##STR47## wherein Ris 3-heptyl or phenyl is approximately 50%. Separation of the aldehydereaction product from the alcohol reactant and recycling of the alcoholreactant will, of course, raise the yield. A higher temperature ofreaction e.g. 500° C. and longer residence time (e.g. greater distanceof travel of reactant through catalyst and/or area of contact withcatalyst) will raise the yield to approximately 80%, the higherresidence time being approximately 20% greater than what is used ineither of Examples III or V.

REACTION SEQUENCE COMMENCING WITH THE USE OF A CARBOXYLIC ACID AS ASTARTING MATERIAL

When commencing with the use of a carboxylic acid as a reactant, forexample in the reaction: ##STR48## whereat the hydroxyalkyl ester ismade directly rather than going through a cyclic acetal followed by anoxidation reaction, although the reaction is more simplified, the yieldswill be necessarily lesser in view of the reaction equilibrium constantbeing lesser.

This reaction is also to take place in the presence of an inert solventsuch as toluene at reflux conditions. Although the nature of theparticular solvent is not critical, too low a boiling point will yieldan unnecessary lengthy period of time of reaction. Accordingly, tolueneis the ideal solvent to use in this reaction in view of its boilingpoint at atmospheric pressure and in view of the fact that it ispreferred to carry out the reaction at temperatures of between 80° and150° C. at atmospheric pressure.

The mole ratio of carboxylic acid:2,2-dimethyl-1,3-propanediol may varyfrom 1:2 up to 2:1 with a preferred mole ratio of carboxylicacid:2,2-dimethyl-1,3-propanediol of 1:2. The esterification reaction isto be carried out in the presence of an esterification catalyst such assulfuric acid or paratoluene sulfonic acid. The concentration ofsulfuric acid catalyst or paratoluene sulfonic acid catalyst in thisesterification reaction may vary from 0.001 molar up to 0.1 molar.

The resulting hydroxyalkyl ester is distilled from the reaction mass inwhich it is formed and either used as is for its organoleptic propertiesor further reacted via an oxidation reaction using air or oxygen in thepresence of a silver or copper chromite catalyst in the apparatus as setforth in FIG. 10 and as described in the Detailed Description of theDrawings, supra. The details of this oxidation reaction are set forthsupra.

Examples of the oxoalkyl esters of our invention and their organolepticproperties are set forth in the following Table I.

                  TABLE I                                                         ______________________________________                                        Structure of                                                                  Oxoalkyl Ester    Organoleptic Properties                                     ______________________________________                                         ##STR49##        Ozoney, aldehydic, floral, green, spicy                                       (coriander-like, cardamom-like, ginger-like).                ##STR50##        A fruity aroma.                                              ##STR51##        A honey, tobacco aroma with coumarin-like, and cumene-                        like notes.                                                  ##STR52##        A fruity, woody aroma.                                      ______________________________________                                    

One or more oxoalkyl esters prepared in accordance with the process ofour invention and one or more auxiliary perfume ingredients including,for example, alcohols other than the oxoalkyl esters of our invention,aldehydes other than the oxoalkyl esters of our invention, ketones,terpenic hydrocarbons, nitriles, esters other than the oxoalkyl estersof our invention, lactones, natural essential oils and syntheticessential oils may be admixed so that the combined odors of theindividual components produce a pleasant and desired fragranceparticularly and preferably in the spice-type fragrances. Such perfumecompositions usually contain (a) the main note or "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main notes; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all states ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low-boiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the oxoalkylester compositions prepared in accordance with the process of ourinvention can be used to alter, modify or enhance the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of the oxoalkyl ester compositions prepared in accordancewith the process of our invention which will be effective in perfumecompositions as well as in perfumed articles (e.g. perfumed polymers,anionic, cationic, nonionic or zwitterionic detergents, soaps, fabricsoftener compositions, fabric softener articles, bath preparations andhair preparations and the like) and colognes depends upon many factorsincluding the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.01% of the oxoalkyl ester compositions prepared inaccordance with the process of our invention or even less (e.g. 0.005%)can be used to impart ozoney, aldehydic, floral, green, spicy(coriander-like, cardamom-like, ginger-like) fruity, honey,tobacco-like, coumarin-like, cumene-like and woody aroma nuances tosoaps, microporous polymers, cosmetics, anionic, cationic, nonionic orzwitterionic detergents, fabric softener compositions, fabric softenerarticles, bath preparations, hair preparations and other products. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations of cost, nature of the end product, the effectdesired in the finished product and the particular fragrance sought.

The oxoalkyl ester compositions prepared in accordance with the processof our invention are useful (taken alone or taken together with otheringredients in perfume compositions) as (an) olfactory component(s) indetergents and soaps, space odorants and deodorants, perfumed polymers,perfumes, colognes, toilet water, bath preparations such as creams,deodorants, hand lotions and sun screens, powders such as talcs, dustingpowders, face powders and the like. When used as (an) olfactorycomponent(s) as little as 0.005% of the oxoalkyl ester compositionsprepared in accordance with the process of our invention will suffice toimpart an ozoney, aldehydic, floral, green, spicy (coriander-like,cardamom-like, ginger-like) fruity, honey, tobacco, coumarin-like,cumene-like and woody aroma to spice formulations and spice-type aromas.Generally, no more than 6% of the oxoalkyl ester compositions of ourinvention based on the ultimate end product is required in the perfumedarticle.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the oxoalkyl estercompositions prepared in accordance with the process of our invention.The vehicle can be a liquid such as a non-toxic alcohol (e.g. ethylalcohol), a non-toxic glycol (e.g. 1,2-propylene glycol) or the like.The carrier can also be an absorbent solid such as a gum (e.g. gumarabic, xanthan gum or the like) or components for encapsulating thecomposition such as gelatin as by coacervation or such as other polymerssuch as urea formaldehyde polymers for the purpose of encapsulation bymeans of formation of capsules having polymeric walls.

It will thus be apparent that the oxoalkyl ester compositions preparedin accordance with the process of our invention can be utilized toalter, modify or enhance the sensory properties particularlyorganoleptic properties, such as as fragrances, of a wide variety ofconsumable materials.

The following Examples I-V set forth means for synthesizing precursorsfor use in synthesizing the products of our invention as well as theproducts of our invention themselves. The examples including VI andsubsequent thereto serve to illustrate the organoleptic utilities of theoxoalkyl esters of our invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of Neopentyl Acetal of Benzaldehyde ##STR53##

Into a 3 liter reaction flask equipped with heating mantle, thermometer,Bidwell trap, reflux condenser, and nitrogen blanket apparatus is placed1000 grams of benzaldehyde (9.4 moles), 1,100 grams of neopentyl alcohol(2,2-dimethyl-1,3-propanediol) (10.5 moles), 250 ml toluene and 10 gramsof paratoluene sulfonic acid. The reaction mass is heated to reflux andrefluxed while removing water at 99°-140° C. for a period of 2.5 hours.At the end of the 2.5 hours, the reaction mass is cooled to roomtemperature, transferred to a separatory funnel and washed as follows:

1. two one-liter volumes of water

2. two one-liter volumes of saturated sodium chloride solution.

The organic layer is then distilled on a 6" stone column yielding thefollowing fractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux                                                                              Fraction                                Number (°C.)                                                                           (°C.)                                                                           mm/Hg  Ratio (grams)                                 ______________________________________                                        1      25/72     10/118  3.0/3.0                                                                              RO                                            2      97       118      3.0    RO     93                                     3      97       118      3.0    RO     97                                     4      97       118      3.0    RO    101                                     5      97       120      3.0    RO    219                                     6      105      123      3.7    RO    225                                     7      105      123      3.8    RO    233                                     8      97       125      3.0    RO    104                                     9      103      128      3.4    RO    114                                     10     109      150      3.0    RO    124                                     11     112      185      3.0    RO    --                                      ______________________________________                                    

Fractions 2-11 are bulked and used for the process of Example II.

FIG. 1 is the GLC profile for the reaction product prior todistillation.

FIG. 2 is the GLC profile for fraction 3 of the foregoing distillation.

FIG. 3 is the NMR spectrum for bulked fractions 2-11 of the foregoingdistillation containing the compound having the structure: ##STR54##

FIG. 4 is the infra-red spectrum for bulked fractions 2-11 of theforegoing distillation containing the compound having the structure:##STR55##

EXAMPLE II Neopentanol Benzoate(2,2-Dimethyl-1,3-Propanediol-Monobenzoate) ##STR56##

Into a 5 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, dropping funnel and cooling bath is placed 310 grams ofacetic acid and 500 grams of benzaldehyde neopentyl acetal having thestructure: ##STR57## prepared in accordance with the process of ExampleI, supra, bulked fractions 2-11. The resulting mixture is cooled to20°-25° C.

Into the dropping funnel is placed 2,200 grams of a 10% solution ofsodium hypochlorite.

Over a period of 4 hours the sodium hypochlorite solution is added tothe mixture of acetic acid and benzaldehyde neopentyl acetal whilemaintaining the temperature of the reaction mass at 20°-29° C., withstirring. At the end of the 4 hour period, the reaction is completed andthe reaction mass is poured into 1,000 ml of a 10% aqueous salt solutionadmixed with 500 ml of methylene chloride. The resulting mixture nowseparates into two phases, an organic phase and an aqueous phase. Theorganic phase is separated from the aqueous phase and the organic phaseis washed with one liter of 5% sodium hydroxide followed by twoone-liter portions of water. The reaction mass is then distilled on a24" Goodloe 1" diameter column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux                                                                              Fraction                                Number (°C.)                                                                           (°C.)                                                                           mm/Hg  Ratio (grams)                                 ______________________________________                                        1      109/120  157/160  .9/.9  9:1/9:1                                                                             21.5                                    2      120      160      .9     9:1   23.8                                    3      120      160      .7     9:1   22.5                                    4      118      159      .6     9:1   17.6                                    5      116      160      .6     4:1   23.2                                    6      116      160      .4     4:1   22.5                                    7      115      161      .3     4:1   19.8                                    8      115      161      .3     4:1   24.5                                    9      115      161      .3     9:1   28.9                                    10     115      161      .3     9:1   22.2                                    11     115      163      .3     9:1   23.3                                    12     120      164      .3     2:1   27.7                                    13     130      167      .3     2:1   61.1                                    14     128      172      .3     2:1   51.0                                    15     103      220      .3     0     47.9                                    ______________________________________                                    

Fractions 2-12 are bulked for use in performing Example III.

FIG. 5 is the GLC profile for the reaction mass prior to distillationcontaining the compound having the structure: ##STR58##

FIG. 6 is the NMR spectrum for bulked fractions 2-11 for the foregoingdistillation containing the compound having the structure: ##STR59##

FIG. 7 is the infra-red spectrum for bulked fractions 2-11 of theforegoing distillation containing the compound having the structure:##STR60##

EXAMPLE III Preparation of 3-Benzoyloxy-2,2-Dimethylpropanal ##STR61##

Using the apparatus of FIG. 10, a catalytic oxidation of alcohol (bulkedfractions 2-11) prepared according to Example II is carried out.Maintaining the silver catalyst and reaction tube at a temperature of450° C. (using furnace 16 and silver catalyst 18 on shaft 19 in reactor17), oxygen held in vessel 120 is permitted to flow at a flow rate of250 ml per minute through regulator 119, filter 118 and mass flowcontroller 117 through heater 112 while at the same time nitrogen at aflow rate of 100 ml per minute is permitted to flow through regulator122, filter 123 and mass flow controller 116 whereupon the nitrogen flowjoins the oxygen flow and the combined gasses (the nitrogen, oxygen andalcohol) are fed through heater 112 into reactor 17. Simultaneously, thebulked fractions 2-11 of the distillation product of Example IIconsisting of the compound having the structure: ##STR62## held inholding tank 101 is pumped through pump 104 into vaporizer 110 throughheating tube 112 along with the oxygen and nitrogen. Simultaneously,water 103 held in holding tank 102 is pumped through pump 105 throughtube 108 into vaporizer 111 and finally through heated tube 112 alongwith the oxygen, nitrogen and alcohol reactant (bulked fractions 2-11 ofthe distillation product of the reaction product of Example IIconsisting of the compound having the structure: ##STR63## and finallyinto the reactor 17 and the silver catalyst 18 at 450° C. The flow rateof the bulked fractions 2-11 of the distillation product of the reactionproduct of Example II containing the compound having the structure:##STR64## is 2 ml per minute (liquid). The liquid flow rate of the wateris also 2 ml per minute.

The reaction product is condensed in heat exchanger 5 and 6 and iscollected at location 1 in flask 2 which is cooled by ice bath 3. Thevolatiles are collected in flask 12 and cooled by dry ice bath 13. Avacuum 14 is supplied wherein the final volatiles are not permitted toescape but are collected at 15.

The detailed description of FIG. 10 is set forth in the section entitled"Detailed Description of the Drawings", supra.

The resulting product is trapped from a 10'×1/4" Carbowax columnprogrammed at 130° C., isothermal.

FIG. 8 is the NMR spectrum for the trap from this GLC, containing thecompound having the structure: ##STR65##

FIG. 9 is the infra-red spectrum for the product trapped from the GLCoperated at the following conditions: 10'×1/4" Carbowax column operatedat 130° C. isothermal, having the structure: ##STR66##

EXAMPLE IV Preparation of 3-Hydroxy-2,2-Dimethylpropyl Ester of 2-EthylHexanoic Acid ##STR67##

Into a 5 liter reaction flask equipped with heating mantle, stirrer,reflux condenser, thermometer and Bidwell trap, is placed 1,456 grams of2,2-dimethyl-1,3-propanediol (14.0 moles); 1,100 ml of 2-ethyl hexanoicacid (7.0 moles), 700 ml toluene and 15 ml 93% concentrated sulfuricacid.

The reaction mass, with stirring, is heated to reflux and maintained atreflux at 126° C. while removing water of reaction. The refluxing iscontinued for a period of 9 hours at which point 300 ml of water hasbeen removed from the reaction mass. When GLC analysis shows that thereaction is complete, the reaction mass is transferred to a 5 literseparatory flask and washed as follows:

(a) three 500 ml volumes of 15% aqueous sodium hydroxide;

(b) two 500 ml volumes of water;

(c) two 500 ml volumes of saturated sodium chloride solution.

The reaction mass is then distilled on a 1" Goodloe column yielding thefollowing fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                        1        28/40   40/95      55/3                                              2        107     128        3                                                 3        109     125        3       98                                        4        110     127        3      112                                        5        121     135        5       89                                        6        124     140        5       97                                        7        126     144        5      204                                        8        128     145        5      206                                        9        134     153        5      198                                        10       145     175        5      130                                        11       155     185        5                                                 12       165     190        5                                                 13       155     220        5                                                 ______________________________________                                    

Fractions 2-9 are bulked for subsequent oxidation.

FIG. 11 is the GLC profile (conditions: SE-30 column programmed at100°-220° C.) for the reaction product prior to distillation.

FIG. 12 is the GLC profile for fraction 3 of the foregoing distillationproduct containing the compound having the structure: ##STR68##

FIG. 13 is the NMR spectrum for bulked fractions 2-9 of the foregoingdistillation containing the compound having the structure: ##STR69##

FIG. 14 is the infra-red spectrum for bulked fractions 2-9 of theforegoing distillation containing the compound having the structure:##STR70##

EXAMPLE V Preparation of 2-Formyl-2-Methyl Propyl Ester of 2-EthylHexanoic Acid ##STR71##

Into a 1 liter reaction flask equipped with cooling bath, stirrer,reflux condenser, thermometer, addition funnel and nitrogen blanketapparatus is placed 200 ml of acetone and 230 grams (1.0 moles) of thebulked fractions 2-9 of the distillation product of the reaction productof Example IV containing the compound having the structure: ##STR72##

Jones reagent (sodium dichromate and sulfuric acid mixture) is added tothe reaction mass slowly over a period of 0.5 hours while maintainingthe mixture at a temperature in the range of 25°-30° C. At the end ofthe addition of the Jones reagent, the reaction mass is stirred at25°-30° C. for a 7 hour period. At the end of the 7 hour period, GLCanalysis indicates 60% conversion.

An additional 100 ml Jones reagent is then added and the reaction massis permitted to exotherm to 51° C. GLC analysis indicates that reactionis complete.

The reaction product is added to 150 ml water and the resulting mixtureis transferred to a separatory funnel. The aqueous phase is extractedwith three 200 ml volumes of diethyl ether and the ether extracts arewashed with three 500 ml portions of water followed by one 500 mlportion of a salt solution. The ether extracts and the organic phase arecombined and the resulting product is stripped of solvent. The resultingproduct is then distilled on a 6" stone mirror column yielding thefollowing fractions:

    ______________________________________                                               Vapor   Liquid                 Weight of                               Fraction                                                                             Temp.   Temp.     Pressure                                                                             Reflux                                                                              Fraction                                Number (°C.)                                                                          (°C.)                                                                            mm/Hg. Ratio (grams)                                 ______________________________________                                        1      66/95   125/142   1.5/2.0                                                                              2:1   20                                      2       93     147       2.0    2:1   21                                      3      104     164       2.0    2:1   --                                      4      140     200       2.0    2:1   --                                      ______________________________________                                    

Fraction 2 having a vapor temperature of 93° C. at 2.0 mm/Hg pressure isanalyzed by means of GLC, NMR and IR analyses which analyses indicatethat the structure of the compound contained therein is: ##STR73##

FIG. 5 is the GLC profile for the reaction product prior to distillation(conditions: SE-30 column programmed at 100°-220° C.). Peak 201 of FIG.15 is the compound having the structure: ##STR74##

FIG. 16 is the GLC profile for fraction 1 of the foregoing distillation(conditions: SE-30 column programmed at 100°-220° C. at 8° C. perminute).

FIG. 17 is the NMR spectrum for the trap of Peak 201 of FIG. 15, the GLCprofile, which is the compound having the structure: ##STR75##

The foregoing reaction can also be carried out using, instead of theJones reagent, oxygen or air as the oxidizing agent and using theapparatus of FIG. 10 as set forth in detail in Example III.

EXAMPLE VI

The following mixture is prepared:

    ______________________________________                                                                       Example                                        Ingredients       Example VI (A)                                                                             VI (B)                                         ______________________________________                                        Phenylacetic acid 70.0         70.0                                           Coumarin          20.0         0                                              Phenylethylphenyl acetate                                                                       100.0        100.0                                          Phenyl ethyl alcohol                                                                            5.0          5.0                                            Benzyl benzoate   100.0        100.0                                          Dimethylphenylethyl                                                           carbinol          10.0         10.0                                           Methyl anthranilate                                                                             5.0          5.0                                            Beta ionone       10.0         10.0                                           Compound having the structure:                                                 ##STR76##                                                                    prepared according to                                                         Example V         0            12.0                                             Compound having the structure:                                               ##STR77##                                                                    prepared according to                                                         Example III       12.0         0                                              ______________________________________                                    

In Example VI(B), the compound having the structure: ##STR78## preparedaccording to Example V imparts the ozoney, aldehydic, floral, green,spicy (coriander-like, cardamom-like and ginger-like) aroma to thishoney formulation.

In Example VI(B), the compound having the structure: ##STR79## impartsthe intense honey, tobacco aroma with coumarin-like and cumene-likenotes and acts as a total replacer for coumarin in this formulation.

The compound having the structure: ##STR80## also acts as a replacer forcumene in those fragrance formulations where cumene has been previouslyused.

EXAMPLE VII Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table II below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table II below.

                  TABLE II                                                        ______________________________________                                        Substance         Aroma Description                                           ______________________________________                                         ##STR81##        An ozoney, aldehydic, floral, green, spicy                                    (coriander-like, cardamom-like and ginger-like) aroma.      prepared according to                                                         Example V                                                                        Compound having the                                                                          A fruity aroma.                                             structure:                                                                     ##STR82##                                                                     ##STR83##        A honey, tobacco aroma with coumarin-like and cumene-                         like nuances.                                                  Compound having the                                                                          A fruity, woody aroma.                                      Structure:                                                                     ##STR84##                                                                      Perfume composition prepared                                                                  A spicy, honey formulation                                  according to Example VI (A).                                                                    with intense coriander-like,                                                  cardamom-like and ginger-like                                                 nuances and floral topnotes                                                   with herbaceous undertones.                                 Fragrance formulation prepared                                                                  A honey, tobacco-like aroma                                 according to Example VI (B).                                                                    with coumarin-like and                                                        cumene-like topnotes.                                       ______________________________________                                    

EXAMPLE VIII Perfumed Liquid Detergents

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976 incorporated by reference herein) with aroma nuances asset forth in Table II of Example VII, are prepared containing 0.10%,0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in TableII of Example VII. They are prepared by adding and homogeneously mixingthe appropriate quantity of substance set forth in Table II of ExampleVII in the liquid detergent. The detergents all possess excellent aromasas set forth in Table II of Example VII, the intensity increasing withgreater concentrations of substance as set forth in Table II of ExampleVII.

EXAMPLE IX Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example VII are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25%, and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample VII are imparted to the colognes and to the handkerchiefperfumes at all levels indicated.

EXAMPLE X Preparation of Soap Compositions

One hundred grams of soap chips (per sample) (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example VII untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example VII.

EXAMPLE XI Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient          Percent by Weight                                         ______________________________________                                        Neodol® 45-11 (a C.sub.15 --C.sub.15                                      alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                       12                                                        Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example VII. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample VII.

EXAMPLE XII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table II of Example VII.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example VII, supra, consist of a substrate coating havinga weight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table II of Example VII isadmixed in each case with the outer coating mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a drier on operation thereof ineach case using said drier-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table II of Example VII,supra.

EXAMPLE XIII Hair Spray Formulations

The following hair spary formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 W.51st St., New York, N.Y. in 91.62 grams of 95% food grade ethanol. 8.0grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Dioctyl sebacate   0.05 weight percent                                        Benzyl alcohol     0.10 weight percent                                        Dow Corning 473 fluid                                                         (prepared by the Dow Corning                                                  Corporation)       0.10 weight percent                                        Tween 20 surfactant                                                           (prepared by ICI America                                                      Corporation)       0.03 weight percent                                        One of the perfumery sub-                                                     stances as set forth in                                                       Table II of Example VII,                                                      supra              0.10 weight percent                                        ______________________________________                                    

The perfuming substances as set forth in Table II of Example VII addaroma characteristics as set forth in Table II of Example VII which arerather intense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XIV Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "Composition A".

Gafquat® 755 N polymer (manufactured by GAF Corporation of 140 W. 51stSt., New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "CompositionB".

The resulting Composition A and Composition B are then mixed in a 50:50weight ratio of A:B and cooled to 45° C. and 0.3 weight percent ofperfuming substance as set forth in Table II of Example VII is added tothe mixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table II of Example VII.

EXAMPLE XV Perfumed Polymer

Scented polyethylene pellets having a pronounced honey aroma wereprepared as follows:

75 pounds of polyethylene of a melting point of about 220° F. wereheated to about 230° F. in a container of the kind illustrated in FIGS.1 and 2 of U.S. Pat. No. 3,505,432, the disclosure of which isincorporated by reference herein. 25 pounds of the honey formulation ofExample VI(A) were then quickly added to the liquified polyethylene, thelid was put in place and the agitating means were actuated. Thetemperature was maintained at about 225° F. and the mixing was continuedfor about 5-15 minutes. The valve was then opened to allow flow of themolten polyethylene enriched with the honey-containing material to exitthrough the orifices. The liquid falling through the orifices solidifiedalmost instantaneously upon impact with the moving cooled conveyor.Solid polyethylene beads or pellets having a pronounced honey scent werethus formed. Analysis demonstrated that the pellets contained about 25%of the honey formulation of Example VI(A) so that almost no losses ofthe scenting substance did occur. These pellets may be called masterpellets.

50 pounds of the honey-containing master pellets were then added to 1000pounds of unscented polyethylene powder and the mass was heated toliquid state. The liquid was molded into thin sheets or films. Thesheets of films had a pronounced honey aroma.

PATENTS INCORPORATED HEREIN BY REFERENCE

The following patents referred to supra are hereby incorporated hereinby reference:

U.S. Pat. No. 3,632,396

U.S. Pat. No. 3,948,818

U.S. Pat. No. 3,505,432

Canadian Pat. No. 1,007,948

What is claimed is:
 1. An oxoalkyl ester defined according to thestructure: ##STR85## wherein Z is a moiety selected from the groupconsisting of carbinol having the structure: ##STR86## andcarboxyaldehyde having the structure: ##STR87## and R is selected fromthe group consisting of 3-heptanyl and phenyl.
 2. The compound of claim1 having the structure: ##STR88##
 3. The compound of claim 1 having thestructure: ##STR89##
 4. The compound of claim 1 having the structure:##STR90##
 5. The compound of claim 1 having the structure: ##STR91##